Desert varnishes are thin, dark mineral coatings found on some rocks in arid or semi-arid environments on Earth. Microorganisms may play an active role in their formation, which takes many hundreds of ... [more ▼]

Desert varnishes are thin, dark mineral coatings found on some rocks in arid or semi-arid environments on Earth. Microorganisms may play an active role in their formation, which takes many hundreds of years. Their mineral matrix may facilitate the preservation of organic matter and is therefore of great relevance to martian exploration. Miniaturized Raman spectrometers (which allow nondestructive analysis of the molecular composition of a specimen) will equip rovers in forthcoming planetary exploration missions. In that context, and for the first time, portable Raman spectrometers operating in the green visible (532 nm as currently baselined for flight) and in the near-infrared (785 nm) were used in this study to investigate the composition (and substrate) of several samples of desert varnish. Rock samples that were suspected (and later confirmed) to be coated with desert varnish were recovered from two sites in the Mojave Desert, USA. The portable spectrometers were operated in flight-representative acquisition modes to identify the key molecular components of the varnish. The results demonstrate that the coatings typically comprise silicate minerals such as quartz, plagioclase feldspars, clays, ferric oxides, and hydroxides and that successful characterization of the samples can be achieved by using flightlike portable spectrometers for both the 532 and 785 nm excitation sources. In the context of searching for spectral signatures and identifying molecules that indicate the presence of extant and/or extinct life, we also report the detection of β-carotene in some of the samples. Analysis complications caused by the presence of rare earth element photoluminescence (which overlaps with and overwhelms the organic Raman signal when a 785 nm laser is employed) are also discussed. Key Words: Desert varnish-Raman spectroscopy-ExoMars-Portable spectrometers-Planetary science. [less ▲]

Raman spectroscopy has been identified as a powerful tool for astrobiology and remote robotic planetary exploration. It can be used to identify and characterise rock matrices, mineral inclusions and ... [more ▼]

Raman spectroscopy has been identified as a powerful tool for astrobiology and remote robotic planetary exploration. It can be used to identify and characterise rock matrices, mineral inclusions and organic molecules and is demonstrablyeffective at identifying biomarkers, or indicators of biological activity. The ExoMars rover, jointly operated by the European and Russian Federal Space Agencies, will carry the first Raman spectrometer into space when it launches in 2018 and two further Raman instruments have recently been announced as part of the payload onboard the National Aeronautics and Space Administration’s Mars 2020 rover. Each of these spectrometers however will, by necessity, have poorer resolution than the most sophisticated laboratory instruments because of mass, volume and power constraints and the space readiness of the requisite technologies. As a result, it is important to understand the minimum instrument specification requiredto achieve the scientific objectives of a mission, in terms of parameters such as spectral resolution and laser footprint size. This requires knowledge of the target minerals and molecules between which there may be ambiguity when identifying bands in spectra from geological samples. Here, we present spectra from a number of Mars analogue samples that include a range of such molecules, highlighting where such confusion may occur and identifying the most useful bands for differentiation. It is recommended that a Ramanspectrometer achieves a resolution of at least 3 cm-1 and covers a spectral range from 100 to 4000 cm-1 in order to differentiate between all of the target molecules presented here. [less ▲]

A simple approach for the production of polymer functionalized graphene nanosheets is reported. The resulting polyacrylonitrile chemisorbed on graphene sheets is made of 1 to 2 layers, with a large ... [more ▼]

A simple approach for the production of polymer functionalized graphene nanosheets is reported. The resulting polyacrylonitrile chemisorbed on graphene sheets is made of 1 to 2 layers, with a large majority of graphene single-layers. This novel functionalized graphene exhibits good cycling stability as an anode in Li-ion batteries without a conductive additive or binder. [less ▲]

Raman spectroscopy has been selected as a non-destructive powerful analytical method for forthcoming planetary exploration. In the context of the upcoming ExoMars and NASA 2020 missions (developed by the ... [more ▼]

Raman spectroscopy has been selected as a non-destructive powerful analytical method for forthcoming planetary exploration. In the context of the upcoming ExoMars and NASA 2020 missions (developed by the European Space Agency, IKI Roscomos and NASA) analysis of the biological and geological terrestrial analogues using laboratory instrumentation is of great importance; especially testing the performance of flight-like operating modes and conditions on the feasibility of flight instruments meeting their science goals. Here we present a set of measurements of terrestrial analogues (among them desert varnishes) selected in preparation for in-situ Raman analysis on Mars. Laboratory instrumentation has been used to fully characterise the samples in addition to being operated in modes consistent with ExoMars RLS instrument flight designs, sample preparation and delivery. We discuss the performance of the spectrometers regarding the detection of the target signatures and their geological context. The impact of instrument operating modes and application of flight instrument sampling philosophy (i.e. spot size, grain size, number of target locations, sample preparation and delivery) on the signal intensity and the limits of detection are also discussed. [less ▲]

in Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences (2014)

The first Raman spectrometers to be used forin situ analysis of planetary material will be launched as part of powerful, rover-based analytical laboratories within the next 6 years. There are a number of ... [more ▼]

The first Raman spectrometers to be used forin situ analysis of planetary material will be launched as part of powerful, rover-based analytical laboratories within the next 6 years. There are a number of significant challenges associated with building spectrometers for space applications, including limited volume, power and mass budgets, the need to operate in harsh environments and the need to operate independently and intelligently for long periods of time (due to communication limitations). Here, we give an overview of the technical capabilities of the Raman instruments planned for future planetary missions and give a review of the preparatory work being pursued to ensure that such instruments are operated successfully and optimally. This includes analysis of extremophile samples containing pigments associated with biological processes, synthetic materials which incorporate biological material within a mineral matrix, planetary analogues containing low levels of reduced carbon and samples coated with desert varnish that incorporate both geo-markers and biomarkers. We discuss the scientific importance of each sample type and the challenges using portable/flight-prototype instrumentation. We also report on technical development work undertaken to enable the next generation of Raman instruments to reach higher levels of sensitivity and operational efficiency. [less ▲]

Recently, matrix‐assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI) has emerged as a powerful technique to study the distribution of lipids. However, quantification still remains a ... [more ▼]

Recently, matrix‐assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI) has emerged as a powerful technique to study the distribution of lipids. However, quantification still remains a challenge because the MALDI signal is strongly affected by ion suppression effects. On the contrary, Raman spectroscopy is recognized as a non‐destructive analysis method and spectral images can also be acquired. The combination of these two techniques was applied for lipids detection in tissue sections. In MALDI, two lipids families (glycerophosphocholine, PC; gycerophosphoethanolamine, PE), three MALDI matrices (1,5‐diaminonapthalene, 1,5‐DAN; 2,5‐dihydroxybenzoic acid, 2,5‐DHB; a‐4‐hydroxicinammic acid, CHCA), and various mixtures of lipids were investigated. The nature of the lipid, as well as the nature of the matrix and the composition of the sample influences the signal of a given lipid. In Raman, despite a strong overlap with the spectrum of the native tissue, an intensity profile constructed along the diameter of the section clearly shows that the signature of one given lipid (a glycerophosphocholine) can be detected on a doped biological sample. [less ▲]

Thein situ control of the chemical composition of industrial aluminum smelter is a challenge mainly for physicochemical reasons: high temperature, high surrounding electromagnetic field, and the highly ... [more ▼]

Thein situ control of the chemical composition of industrial aluminum smelter is a challenge mainly for physicochemical reasons: high temperature, high surrounding electromagnetic field, and the highly corrosive molten salt electrolyte to deal with. In previous works, we proposed that Raman spectroscopy is a method of choice that could be adapted to real smelters. The laboratory study presented here relies on reproducible Raman spectra recorded on molten mixtures whose compositions are identical to those used during the production of aluminum. A normalization procedure for the Raman spectra is proposed based on the equilibria taking place in the bath. In addition, we discuss two quantitative models to determine the alumina content from the Raman spectra of the molten NaF−AlF3−CaF2−Al2O3 electrolytes. Univariate and multivariate approaches are applied to determine both theCOx (alumina content) and the CR (NaF/AlF3 molar ratio) by Raman spectroscopy without referring to an additional internal reference of intensity. The procedure was successfully tested and validated on industrial samples. [less ▲]

Worldwide metallic aluminium production involves the Hall-Héroult process where the metal is electro-deposited from aluminium oxide solubilised in a molten NaF-AlF3-CaF2 mixture at around 950°C. The ... [more ▼]

Worldwide metallic aluminium production involves the Hall-Héroult process where the metal is electro-deposited from aluminium oxide solubilised in a molten NaF-AlF3-CaF2 mixture at around 950°C. The cryolitic melt is conveniently characterised by both the molar NaF/AlF3 ratio and the Al2O3 content. Nowadays the Hall-Héroult process remains the more economically efficient process even if it still suffers from a high consumption of energy. In particular the overvoltage required by the electrolysis is strongly dependent on the melt composition, especially regarding the Al2O3 content. Controlling the industrial baths composition during the process is therefore critical to reduce the energy loss. Unfortunately there is, up to now, no in situ direct analytical method to do so. Considering our experience in the study of such highly corrosive media by Raman spectroscopy, that technique has been applied to directly determine the melt composition. Three sets of reference spectra are considered in this study, each of them recorded with a different setup. The employed setups were developed to reach progressively, at the laboratory scale, a design that is suitable for a plant application. Eventually, a high quality spectrum can be recorded by the top of the melt, in less than 20 seconds. The employed apparatus is found to influence significantly the shape and quality of the spectra, and consequently their involvement in the quantification. A complex digital treatment of the spectral data acquired is necessary because all Raman bands of interest strongly overlap and some are situated close to the Rayleigh decay. Two main quantitative procedures for the melt composition determination are studied. The first one, the AutoAnalysis procedure, developed in the past and adapted here to the new data, gives reliable predictive results for both the NaF/AlF3 molar ratio and the alumina content. They can be determined with an absolute deviation of 0.06 molar ratio unit and 0.5 wt% respectively. However, the intensity normalisation, required for comparing the intensities of different spectra, relies on the Rayleigh decay that is likely to change with the experimental conditions in the plants. In our second quantitative procedure, the NormaAnalysis procedure, the intensity normalisation is based on the equilibria taking place in the melt. Since those equilibria do no differ with the experimental setup, the NormaAnalysis procedure can be imported to the industrial field. The predicted composition is also evaluated with a good precision: the NaF/AlF3 molar ratio and the alumina content can be determined with an absolute deviation of 0.08 cryolitic ratio unit and 0.3 wt% respectively. It is concluded that the composition of the melt can now be determined with our NormaAnalysis procedure, from a single Raman spectrum, recorded with a Raman apparatus exportable for an in situ measurement on the industrial cells. [less ▲]

Phospholipids, PL, such as the phosphatidylcholine PC(18:0/18:1), play a role in the structure of living cells and are suspected to be part of the development of some diseases, for example cancers. Mass ... [more ▼]

Phospholipids, PL, such as the phosphatidylcholine PC(18:0/18:1), play a role in the structure of living cells and are suspected to be part of the development of some diseases, for example cancers. Mass spectrometry enables the structural analysis of PL in complex biological media but imaging mass spectrometry by MALDI-MS is rather limited for quantification purposes. Complementarily, Raman spectroscopy as a non invasive and non destructive method is a potential candidate to quantify and visualise the spatial distribution of the PL by molecular imaging. Unfortunately, the lack of specific chemical function in PL, compared to others biomolecules, limits the use of Raman spectroscopy in the identification process of those PL in complex biological samples. The results presented here belong to a first study of the application of the Raman analyses on dried residues of PL and mice brain tissue performed in the lab. [less ▲]

For the last 40 years, Raman spectroscopy has been very useful in investigating the structure of corrosive molten salts, such as the cryolite-based melts widely used as electrolyte in the Hall-Heroult ... [more ▼]

For the last 40 years, Raman spectroscopy has been very useful in investigating the structure of corrosive molten salts, such as the cryolite-based melts widely used as electrolyte in the Hall-Heroult process. Even if this process remains the most economically efficient for metallic aluminum electro-production, it suffers from a high energy loss, which is dependent on the melt composition. Therefore, controlling the chemical composition of the electrolyte is essential. The present paper proposes to apply Raman spectroscopy for the direct determination of the NaF-AlF3 molar ratio in NaF-AlF3-CaF2-based melts. Despite the experimental difficulties, a calibration curve based on equilibria taking place in the melt has been developed and the procedure has been successfully compared to industrial samples of known compositions. The possible exportation of the laboratory scale procedure to an industrial environment application for the control of the Hall-Heroult process is finally discussed. [less ▲]

This work investigates the possibility to prepare mesoporous thin films of Li-Ti, Li-Nb, Li-Nb-V and Li-V oxides through a direct sol-gel EISA route by dissolving a lithium salt in the precursor solution ... [more ▼]

This work investigates the possibility to prepare mesoporous thin films of Li-Ti, Li-Nb, Li-Nb-V and Li-V oxides through a direct sol-gel EISA route by dissolving a lithium salt in the precursor solution. Experimental conditions involve a hydrolysis molar ratio H2O/TM ~10 (TM = Ti,Nb,V) and the common Pluronic structuring agent P123 (EO20-PO70-EO20). Systematic formation of lithium-containing oxides as first-crystallizing phases points to a significant intermixture of lithium and transition metal ions in the inorganic network. In the case of Ti-based and Nb-based oxide films, addition of lithium to the precursor solution is compatible with the formation of amorphous mesoporous films at 350°C. On the contrary, addition of lithium has a detrimental effect on the notoriously difficult formation of vanadium-based mesostructured films: even when replacing half of the vanadium by niobium as a stabilizer, formation of mesostructured films has not been possible in the investigated range of experimental conditions. [less ▲]

We present here the results obtained during our tentative to analyse quantitatively dried drops of phospholipidic solutions by Raman spectroscopy. Drops of different solutions of phospholipid were deposed ... [more ▼]

We present here the results obtained during our tentative to analyse quantitatively dried drops of phospholipidic solutions by Raman spectroscopy. Drops of different solutions of phospholipid were deposed onto different material supports. The spots were then analyses by confocal Raman microspectroscopy. Experimental settings have been optimised and the analysis of the intensity profile of the Raman signal inside the spot allows the establishment of a calibration curve for the determination of the phospholipids amount within a 1 µL solution. [less ▲]

in Chemphyschem : A European Journal of Chemical Physics and Physical Chemistry (2012), 13(11), 2666-2670

A novel setup is described to monitor the kinetics of homogeneous and heterogeneous reactions online using Raman spectroscopy under high pressure. The arrangement is based on a high-pressure reactor ... [more ▼]

A novel setup is described to monitor the kinetics of homogeneous and heterogeneous reactions online using Raman spectroscopy under high pressure. The arrangement is based on a high-pressure reactor equipped with a sapphire window in combination with a mobile probe that allows the collection of the back-scattered Raman signal at 360°. [less ▲]

Considering our experience in the study of such highly corrosive media by Raman spectroscopy and since the bath spectrum is function of the molar NaF/AlF3 ratio and the Al2O3 content, we have proposed in ... [more ▼]

Considering our experience in the study of such highly corrosive media by Raman spectroscopy and since the bath spectrum is function of the molar NaF/AlF3 ratio and the Al2O3 content, we have proposed in the past to apply that technique to the direct determination of the melt composition . Recent instrumental developments on CCD based spectrometers have made the proposed method more feasible. This presentation will first demonstrate that, employing an updated instrument provided with new optical filters and a more sensitive CCD detector, better quality spectra are obtained. Afterward, new results relevant to the development of our analytical method for the direct determination of the molar NaF/AlF3 ratio and the Al2O3 content in cryolitic melt will be discuss. Different aspects of the calculation procedure will be illustrated:  Estimation and subtraction method of the Rayleigh decay from melt spectra;  Development of an internal normalisation procedure based on equilibria in the melt and assisted by home-made software;  Establishment of calibration curves for the determination of the molar ratio NaF/AlF3 in the melt;  Establishment of calibration curves for the determination of oxide content in the melt;  Overall procedure for the composition determination. [less ▲]

Surface-charged nanofibers were prepared by electrospinning technique (ESP). For this purpose, a copolymer bearing carboxylic acid functions was added to a poly(D,L-lactide) solution just before ESP ... [more ▼]

Surface-charged nanofibers were prepared by electrospinning technique (ESP). For this purpose, a copolymer bearing carboxylic acid functions was added to a poly(D,L-lactide) solution just before ESP process. In a basic medium, negative charges were therefore revealed on fiber surface. By deposition of positively charged particles or polyelectrolytes, surface properties of the fibers could be tailor-made for a specific application. This versatile method can, for example, be applied to the preparation of new biomedical scaffolds. [less ▲]

Since the end of the nineteenth century, metallic aluminium is produced by electro-deposition from a solution of aluminium oxide in cryolitic melts around 1000°C (Hall-Héroult process). The industrial ... [more ▼]

Since the end of the nineteenth century, metallic aluminium is produced by electro-deposition from a solution of aluminium oxide in cryolitic melts around 1000°C (Hall-Héroult process). The industrial melt is composed mostly of cryolite (Na3AlF6) and AlF3 and is characterized by the molar NaF/AlF3 ratio, named cryolitic ratio (CR). It turns out that the bath composition is critical: for instance, it has been shown that a small change in the Al2O3 content leads to a great change in the overvoltage required for the electrolysis. Therefore controlling the melt composition is very important in order to reduce the energy lost. Unfortunately no in situ analytical method allows studying the composition of the melt yet. Considering our experience in the study of such highly corrosive media by Raman spectroscopy and since the bath spectrum is function of both the CR and the Al2O3 content, we have proposed in the past to apply that technique to the direct determination of the melt composition. Despite the CR could be well evaluated in the lab, experimental problems however made the practical application difficult. The purpose of this presentation will be to show the new results obtained on an updated instrument: - Spectra are recorded in 20 s or less with a higher quality than before. - The previously developed home-made software was adapted to the updated instrument and various spectra analysis procedures are under study. - A procedure to prepare reference samples was also developed taking into account the homogeneity problems that have been met. - The slopes of the alumina calibration curves are depending on the bath CR, in confirmation of our previous results. - The new results are compared with the previous ones. It will be concluded that Raman spectroscopy is indeed becoming a suitable technique for developing an analytical method to determine the composition of industrial cryolitic melts. [less ▲]